Quaternary amino alcohol functional organosilicon compounds, composition containing the latter and their production and use

ABSTRACT

The invention relates to novel quaternary amino alcohol functional organosilicon compounds, aqueous compositions containing the latter, and a method for their production, in particular in the form of oligomers and polymers which can be present in the partially or fully hydrolyzed form and are in particular water-soluble. The compositions comprise only an extremely small portion of VOCs. The invention further relates to their use, preferably in the production of inkjet photographic papers.

The invention relates to new quaternary-amino alcohol-functional,organosilicon compounds, to aqueous compositions comprising them, and toprocesses for their preparation, more particularly in the form ofoligomers and polymers, which may be in partly hydrolyzed to fullyhydrolyzed form, and more particularly are water-soluble. Thecompositions have an extremely low VOC fraction. Further described istheir use, more particularly—though not exclusively—for cationicmodification of inorganic or polar organic surfaces, as for examplefillers, pigments, glass, mineral and ceramic surfaces, synthetic andnatural polar materials, such as, for example, polyesters, polyamides,wool, silk, cellulose, lignocellulose, wood, proteins, sugars,polysaccharides, and the like, which may also be present in particulateform or fiber form, in the cm, mm, micronized or else nanometric range,in papercoating slips, for cationization of inkjet coatings, preferablyin the production of inkjet photographic papers, for finishing fibermaterials and/or textiles, for improving the colorability of substrates,as for example in the case of textile fibers, yarns, paper, films orelse correspondingly coated substrates, for inhibiting or suppressingthe growth of microorganisms or of an electrostatic charge buildup, togive but a few particularly advantageous possibilities for application.

Generally speaking, organofunctional alkoxysilanes with quaternarynitrogen functionality, i.e., with a cationic group comprising anorganofunctionalized nitrogen, have been known for some time. Thequaternary nitrogen has a cationic functionality independently of thepH. Their preparation to date was possible only via costly andinconvenient processes, as for example under elevated pressure in anautoclave. A further disadvantage of these alkoxysilanes is the releaseof hydrolysis alcohols into the environment when using the knownwater-based application solutions.

The preparation of cationic organosilanes and their partial use inaqueous phases is reported in the documents which follow. DE 881654discloses the preparation of quaternary silanes in an autoclave underanhydrous conditions. Further processes are disclosed by NL 6517163 forpreparing quaternary methylaryl silanes; DE 1262272 discloses thepreparation of corresponding silicones. DE 2221349, DE 2648240, U.S.Pat. No. 4,035,411, U.S. Pat. No. 4,005,118 and U.S. Pat. No. 4,005,119disclose processes for preparing quaternary silanes.

WO 2008/004243 discloses water-soluble silanes with quaternary aminofunctionality. The water solubility is achieved by esterification withglycols, which in the course of the hydrolysis, i.e., of the“dissolution” of the silanes in water, are released and so give rise toa considerable contamination of the aqueous solution with additionalorganic components, which are commonly viewed as organic solvents.

The use of quaternary amino-functional alkoxysilanes for inhibiting thegrowth of microorganisms is described by DE 2222997, DE 2229580 and DE2408192. Improved colorability of materials which are difficult tocolor, such as Teflon or else leather, through use of correspondingsilanes is disclosed by GB 882067. The preparation ofquaternary-functionalized organosilanes takes place in each case inaprotic organic solvents or under moisture exclusion and elevatedpressure. The silanes prepared by these processes, or aqueousformulations of said silanes, contain large quantities of solvent. Inmany applications this leads to considerable disadvantages, such as alow flashpoint, necessitating explosion protection measures, orenvironmental damage caused by a high VOC burden.

WO 2008/076839 uses a commercially available quaternary silane (AEM5772, Aegis antimicrobial agent, active ingredient:3-(trimethoxysilyl)propyldimethyl-octadecylammonium chloride),containing 12% of methanol. U.S. Pat. No. 4,845,256 discloses a processfor preparing quaternary silanes alkaline earth metal iodide catalystsfor the reaction of chloroalkyl-functional alkoxysilanes and tertiaryamines. The process described proceeds under atmospheric pressure at atemperature of 100° C., but is disadvantageous in two respects. First,alkaline earth metal iodides, which are problematic for the environment,are used in considerable quantities, and secondly the aqueousapplication solutions include considerable quantities of VOC, such ashydrolysis methanol and glycols, which are used in the process there andremain in the application solution. In an aqueous application solution,the product described in example 1 generates more than 50% of VOC (basedon the as-used solution of the quaternary methoxysilane[3-(trimethoxysilyl)propyldecyldimethylammonium chloride] in solution inpropylene glycol monomethyl ether).

The documents below disclose the use of cationic amino-functionalsilanes for the cationization of inkjet paper applications.

WO 2005/009745 A2 discloses cationic aluminum oxide particles withamino-functional silanes. US 20030175451 relates to the coating ofsilica with silanes for the purpose of improving performance in inkjetapplications. US 20050170109 discloses the treatment of silica withaminoalkoxysilanes and use thereof for inkjet papers and DE 10 2007012578 A1 discloses the preparation of cationic silica dispersions usingprimary, secondary or tertiary aminosilanes, and the use thereof forcoatings. WO 2005/009745 A2, US 2005/170109 A1, and US 2003/175451 refergenerally to the possibility of using a quaternary amino-functionalalkoxysilane, such as trimethoxysilanepropyl-N,N,N-trimethylammoniumchloride, or a N,N,N-tributylammonium chloride-substituted silane.Concrete examples are not disclosed.

DE 102007040802 A1 describes the successful use of low-VOC, protonatedamino-functional siloxane systems containing silanol groups (Hydrosils)in the cationization of papercoating slips. The protonation of the aminofunction in these systems is heavily pH dependent. Consequently, theperformance of these applications is still in need of improvement. Theprocessing properties of papercoating slips are governed by theirviscosity and solids content. The higher the viscosity, the greater thecost and inconvenience of processing, although at the same time a highsolids content is desired for the systems for capacity reasons.

DE 10 2009 002 477.8 or PCT/EP2010/053626 reveals the reaction ofchloropropyltriethoxysilane and tetramethylethylenediamine for thepreparation of siloxane systems.

There therefore continues to be a need for reduced-VOCquaternary-amino-functional, organosilicon compounds, which allow thesetting of a low viscosity in conjunction with high solids content fordispersions, as for example silica dispersions, more particularlypapercoating slips. The water solubility thereof and VOC content of theorganosilicon compounds ought preferably to be improved relative toknown systems, and silica dispersions with a low coarse fraction oughtpreferably to be accessible.

The problem addressed by the present invention was that of providingVOC-reduced, quaternary-amino alcohol-functional, organosiliconcompounds, and compositions comprising them, and VOC-containingintermediates thereof, and also an economic process for theirpreparation, which preferably allows the desired viscosity and thesolids content to be set economically in the process.

The problem is solved in accordance with the invention as detailed inthe claims. More particularly, the problem is solved by thequaternary-amino alcohol-functional, organosilicon compounds of theinvention and also by the comprising composition in accordance with thefeatures of the independent claims, and also by the preparationprocesses of the invention in the independent claims. Preferredembodiments are set out in the dependent claims and also in thedescription.

The problem has surprisingly been solved by reactinghaloalkyl-functional alkoxysilanes with tertiary amino alcohols in thepresence of or with the addition of a defined amount of water, orcarrying out reaction waterlessly to start with and subsequently with adefined amount of water, and at least partly removing the hydrolysisalcohol formed, the hydrolysis alcohol preferably being removedsubstantially completely. The quaternization reaction and at leastpartial hydrolysis and optional partial condensation that take placeadvantageously are carried out under temperature control—in other words,according to the requirement, heating or cooling takes place, and thereaction mixture is also stirred appropriately. In the course of thisprocedure, an originally tertiary-substituted nitrogen atom in the aminoalcohol is transformed into a quaternary nitrogen atom, moreparticularly with formation of inventively obtainable oligomeric and/orpolymeric, quaternary-amino-functional organosilicon compounds, whichare elucidated in more detail below. A particular surprise and advantageis that there is no need to use a catalyst for the quaternizationreaction, for the hydrolysis and/or condensation. Moreover, with regardto the viscosity of the present systems, it was a surprise and advantagethat no esters of the silanol groups with amino alcohol groups areformed under the process conditions.

The invention advantageously enables the provision of new VOC-reduced(volatile organic compound) quaternary-amino alcohol-functional,organosilicon compounds, which advantageously can be provided in highyield and under atmospheric pressure. The organosilicon compounds of theinvention may have linear, branched and/or cyclic structures and/orstructural regions with M, D, and/or T structures. Quaternary-aminoalcohol-functional, organosilicon compounds of the invention and alsocorresponding aqueous compositions which comprise at least one of thequaternary-amino alcohol-functional, organosilicon compounds of theinvention can be employed advantageously, with particular advantage forthe provision of very low-VOC, low-viscosity silica dispersions for theproduction of papercoating slips, and more particularly dispersions ofthis kind with a comparatively low coarse fraction.

A further surprise associated with the reaction according to theinvention is that the stated reactions, such as quaternization,hydrolysis, and preferably condensation, can be carried out almostsimultaneously in a reaction mixture at relatively low reactiontemperatures of below 100° C. and hence with particular advantage. Afurther particular advantage of the process of the invention is that thereaction can proceed at these relatively low temperatures underatmospheric pressure. In the process of the invention it is thereforepossible, preferably, to do without the use of autoclaves which areexpensive and inconvenient to operate, since, depending on the tertiaryamino alcohols used and on their boiling point, the reaction is carriedout advantageously under atmospheric pressure, if the boiling point ofthe amines is above the reaction temperature. The boiling point of thetertiary amino alcohols used, more particularly those of the formulaIII, is preferably, as elucidated below, above 85° C., more preferablyabove 100° C., more particularly above 120° C.

Thus it is particularly surprising that not only the quaternizationreaction on the haloalkyl group of the haloalkyl-functional silane ofthe formula II that is used, but also the hydrolysis and also thecondensation or co-condensation of the compounds II and/or IV present inthe reaction mixture, and/or their hydrolysis products, proceeds notonly simultaneously, i.e. in the form of a one-pot reaction, butfurthermore, largely selectively as well.

The invention provides quaternary-amino alcohol-functional,organosilicon compounds, comprising quaternary-amino alcohol-functionalsilanols and also quaternary-amino alcohol-functional siloxanololigomers with Si—O-crosslinked structural elements (hereinafter alsocalled, for short, silanols and also siloxanol oligomers), which formcatenate, cyclic and/or crosslinked structures and which are obtainablefrom a reaction of at least one silane of the formulae II, IV or atleast one hydrolysis, condensation or co-condensation product startingfrom silanes of the formula II and/or IV, water and at least one aminoalcohol of the formula III and optionally the hydrolysis alcohol formedin this reaction is at least partly removed from the system,

-   -   where at least one structure of said quaternary-amino        alcohol-functional, organosilicon compounds corresponds in        idealized form to the general formula I,

(R¹O)[(R¹O)_(1-x-y)(R²)_(x)Si(C⁺)_(1+y)O]_(a)R¹ [a·(1+y)]Hal⁻  (I)

where C⁺ in formula I is independently a group of the formula V

[—(R³)_(n)CH₂—N⁺[—(CH₂)_(m)OH]_(z)(R⁴)_(3-z)]_(1+y)  (V),

-   -   in formula I, R¹ independently of one another are hydrogen or a        linear, branched or cyclic alkyl group having 1 to 8 C atoms,        more preferably R¹ is substantially hydrogen and optionally a        corresponding alkyl group, R² are identical or different and R²        is a linear, branched or cyclic alkyl group having 1 to 8 C        atoms or is an aryl, arylalkyl or acyl group,    -   in formula V R³ are identical or different and R³ is a linear,        branched or cyclic alkylene group having 1 to 18 C atoms, R⁴ are        identical or different and R⁴ is a group comprising C1 to C16        atoms, more particularly R⁴ is a hydrocarbon group, preferably        an alkyl group having 1 to 16 C atoms, more preferably having 1        to 7 C atoms,    -   in formulae I and V, independently, n is 0 or 1, m is an integer        between 1 and 16 and z is 1 or 2 or 3, and Hal is chloro or        bromo, and x is 0 or 1, y is 0 or 1 and (x+y) is 0 or 1, and a        is greater than or equal to 1, more particularly greater than or        equal to 2, more particularly greater than or equal to 4,    -   where the silane of the formula II is a haloalkylsilane,

(R¹0)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂Hal]_(1+y)  (II),

and the silane of the formula IV is a quaternary-aminoalcohol-functional, organosilicon compound

(R¹0)_(3-x-y)(R²)_(n)Si[R³)_(n)CH₂—N⁺[—(CH₂)_(m)OH]_(z)(R⁴)_(3-z)]_(1+y)·(1+y)[Hal⁻]  (IV),

and the amino alcohol corresponds to the formula III,

[HO—(CH₂)_(m)—]_(z)N(R⁴)_(3-z)  (III),

-   -   where in the formulae II, III and/or IV, independently groups R¹        are identical or different and R¹ is a hydrogen, a linear,        branched or cyclic alkyl group having 1 to 8 C atoms, or an        aryl, arylalkyl or acyl group, groups R² are identical or        different and R² is a linear, branched or cyclic alkyl group        having 1 to 8 C atoms or is an aryl, arylalkyl or acyl group,        R³, R⁴, Hal and also n, m and z, independently of one another,        are as defined above, and x is 0, 1 or 2, y is 0, 1 or 2 and        (x+y) is 0, 1 or 2.

Preferred siloxanol oligomers, more particularly of the general formulaI shown only in idealized form, have a high fraction of D structures andT structures of in each case more than 10% (²⁹Si—NMR). They maypreferably have between 30% to 60% D structures and 30% to 60% Tstructures, more particularly of in each case around 40 to 55%, morepreferably in each case around 40% to 50%, with 100% being achieved intotal with silanes and with M structures, which are present only to aminor extent. (Regarding the definition of M, D, and T structures, seeWalter Noll, Chemie and Technologie der Silicone [Chemistry andTechnology of Silicones], 1968, Verlag Chemie GmbH, Weinheim, chapter1).

Here m is preferably 1, 2, 3, 4, 5, 6 or 7 and R⁴ is a group comprising1, 2, 3, 4, 5, 6 or 7 C atoms, more preferably m is 1, 2 or 3,inventively m is 2; and R⁴ is a linear, branched or cyclic alkyl grouphaving 1 to 16 C atoms, more particularly an alkyl group having 1 to 7 Catoms, preferably an alkyl group having 1 to 6 C atoms, more preferablyhaving 1 to 4 C atoms, and this group furthermore may be substituted, inwhich case optionally two groups R⁴ are in turn linked to one anotherand form a ring system with the nitrogen of the tertiary amine.

In accordance with the invention, the quaternary-aminoalcohol-functional organosilicon compounds in the form of siloxanololigomers, such as formula I, where with particular preference R¹corresponds substantially to hydrogen, are water-soluble; advantageouslythe compounds of the formula IV are water-soluble as well.

In accordance with the invention, use is made as amino alcohols of theformula III preferably of N,N-dimethylethanolamine,N,N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine,triethanolamine or at least two of the aforementioned compounds.

The pure quaternization reaction of compounds of the formula II or asper component A, and of the tertiary amino alcohol of the formula III asper component B, to give at least one quaternary-aminoalcohol-functional, organosilicon compound of the formula I and/or IV isset out in a model basis below, with the formulae II and III beingdefined as above:

Furthermore, during the reaction, by hydrolysis and also condensation ofcompounds of the formulae II and/or resultant quaternization products(IV), it is possible for what are called oligomeric and/or polymeric,quaternary, amino alcohol-functional, organosilicon compounds,comprising silanols and/or substantially siloxanol oligomers, to beformed as are elucidated below. Here, of course silanols and/orsiloxanol oligomers that are present may also contain Si-bonded alkoxygroups; in this regard, see also formula I.

Hence in accordance with chemical understanding it is assumed that underthe reaction conditions according to the invention, the reaction ofcompounds of the formulae II and III proceeds with quaternization and atleast partial hydrolysis, as illustrated on a model basis below using3-chloropropyltriethoxysilane (CPTEO) and N,N-dimethylethanolamine,without confining the model thereto.

Quaternization and partial or complete hydrolysis:

Cl—(CH₂)₃—Si(OEt)₃+[HO—(CH₂)₂—]N(CH₃)₂+H₂O->(EtO)₂(HO)Si[—(CH₂)₃—N⁺[—(CH₂)₂OH](CH₃)₂]·Cl⁻+EtOH

Cl—(CH₂)₃—Si(OEt)₃+[HO—(CH₂)₂—]N(CH₃)₂+2H₂O->(EtO)(HO)₂Si[—(CH₂)₃—N⁺—[(CH₂)₂OH](CH₃)₂]·Cl⁻+2 EtOH

Cl—(CH₂)₃—Si(OEt)₃+[HO—(CH₂)₂—]N(CH₃)₂+3H₂O->(HO)₃Si[—(CH₂)₃—N+⁺[—(CH₂)₂OH](CH₃)₂]·Cl⁻+3 EtOH

Condensation:

x(HO)₃Si[—(CH₂)₃—N⁺[—(CH₂)₂OH](CH₃)₂]·Cl⁻->[(HO—)₂Si[—(CH₂)₃—N⁺[—(CH₂)₂OH](CH₃)₂]]—[O—Si[—(CH₂)₃—N⁺[—(CH₂)₂OH](CH₃)₂](OH)]_(x-2)—[O—Si[—(CH₂)₃—N⁺[—(CH₂)₂OH](CH₃)₂](OH)₂]·xCl⁻ +x H₂O

Depending on the degree of hydrolysis, there may also be alkoxy groupsinstead of hydroxyl groups. In that case x may be a number form 2 to ∞.

The invention also provides a process for preparing a compositioncomprising quaternary-amino alcohol-functional, organosilicon compounds,comprising quaternary-amino alcohol-functional silanols and alsosiloxanol oligomers, and also compositions obtainable by this process,preferably a composition comprising quaternary-amino alcohol-functionalsiloxanol oligomers, by reacting

-   -   as component A        -   (i) at least one haloalkyl-functional alkoxysilane of the            general formula II

(R¹0)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂Hal]_(1+y)  (II),

-   -   in which groups R¹ are identical or different and R¹ is a        hydrogen, a linear, branched or cyclic alkyl group having 1 to 8        C atoms, or an aryl, arylalkyl or acyl group, and groups R² are        identical or different and R² is a linear, branched or cyclic        alkyl group having 1 to 8 C atoms or is an aryl, arylalkyl or        acyl group, groups R³ are identical or different and R³ is a        linear, branched or cyclic alkylene group having 1 to 18 C        atoms, n is 0 or 1 and Hal is chloro or bromo, and x is 0, 1 or        2, y is 0, 1 or 2 and (x+y) is 0, 1 or 2,    -   or    -   (ii) a hydrolysis or condensation product of at least one        alkoxysilane of the aforementioned general formula II,        hydrolysates and/or homocondensate or mixtures of at least two        alkoxysilanes of the formula II thereof,    -   or    -   (iii) a mixture of at least one alkoxysilane of the        aforementioned general formula II and a hydrolysis and/or        condensation product of at least one alkoxysilane of the        aforementioned general formula II        -   with a tertiary amino alcohol of the general formula III as            component B,

[HO—(CH₂)_(m)—]_(z)N(R⁴)_(3-z)  (III),

-   -   in which groups R⁴ are identical or different and R⁴ is a group        comprising C1 to C16 atoms, m is an integer between 1 and 16,        more particularly is a hydrocarbon group or alkyl group as        defined above, and z is 1 or 2 or 3; preferably m is 1 to 7 and        R⁴ is a group comprising C1 to C7 atoms, more preferably m is 1,        2 or 3, inventively m is 2; and R⁴ is a linear, branched or        cyclic alkyl group having 1 to 16 C atoms, more particularly an        alkyl group having 1 to 7 C atoms, preferably an alkyl group        having 1 to 6 C atoms, more preferably having 1 to 4 C atoms,        which may, furthermore, be substituted, in which case optionally        two groups R⁴ are internally linked to one another and form a        ring system with the nitrogen of the tertiary amine; with        particular preference the amino alcohol is        N,N-dimethylethanolamine, N,N-diethylethanolamine,        N-methyldiethanolamine, N-ethyldiethanolamine, triethanolamine        or a mixture comprising at least two of the compounds,        -   wherein the process is carried out in at least one step in            the presence, and/or more particularly with addition, of a            defined amount of water, and        -   optionally the hydrolysis alcohol formed is removed at least            partly from the system; preferably hydrolysis alcohol formed            and also any solvent added are substantially completely            removed.

In accordance with preferred process variants, the reaction of componentA and of component B is carried out in the presence of a defined amountof water or component A is reacted with component B and the product issubsequently hydrolyzed in the presence of a defined amount of water;preferably, in component A, more particularly of the formula II, R¹ isalkyl having 1 to 4 C atoms, acyl, and R³ is a linear alkylene grouphaving 1, 2, 3, 4, 5, 6, 7 C atoms, preferably having 2 C atoms.

In accordance with the invention, use is made as component A of at leastone silicon compound selected from 3-chloropropyltrimethoxysilane,3-chloropropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane,3-chloropropylmethyldiethoxysilane, 3-chloropropyldimethylethoxysilaneor 3-chloropropyldimethylmethoxysilane or a hydrolysis or condensationproduct of the aforementioned alkoxysilanes.

In the process of the invention it is particularly preferred to use ahaloalkyl-functional silane of the formula II selected from thefollowing group:

chloropropyltrimethoxysilane, chloropropyltriethoxysilane,chloropropylmethyldimethoxysilane and chloropropylmethyldiethoxysilaneand/or the hydrolysis and/or condensation product thereof.

In preferred processes, R³ in formula II or IV is a linear, branchedand/or cyclic alkylene having 1 to 18 C atoms, more particularly amethylene (—CH₂—), ethylene [—(CH₂)₂—], propylene [—(CH₂)₃-], butylene[—(CH₂)₄— or —(CH₂)CH(CH₃)(CH₂)—], and n=0 with Hal being chloro. Withparticular preference the moiety —[(R³)_(n)CH₂Hal] is a chloromethylene,chloroethylene, 3-chloropropylene, 2-chloropropylene,2-chloroisopropylene, chlorobutylene, chloroisobutylene, chloropentyl,chlorohexyl, chlorocyclohexyl, chloroheptyl, chlorooctyl,chloro-n-octyl, chlorocyclooctyl group. Other haloalkylsilanes of theformula II that can be used in the process of the invention are selectedmore particularly from the group consisting of3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane,3-chloropropyltripropoxysilane, chloropropylmethyldimethoxysilane,chloropropylmethyldiethoxysilane, chloropropyldimethylethoxysilane,chloropropyldimethylmethoxysilane, chloroethyltrimethoxysilane,chloroethyltriethoxysilane, chloroethylmethyldimethoxysilane,chloroethylmethyldiethoxysilane, chloroethyldimethylmethoxysilane,chloroethyldimethylethoxysilane, chloromethyltriethoxysilane,chloromethyltrimethoxysilane, chloromethylmethyldimethoxysilane,chloromethylmethyldiethoxysilane, chloromethyldimethylmethoxysilane,chloromethyldimethylethoxysilane,2-chloroisopropyltris(methoxyethoxy)silane,3-chloropropylcyclohexyldiethoxysilane,3-chloroisobutyltrimethoxysilane, 3-chloroisobutyltriethoxysilane,3-chloropropylcyclohexyldimethoxysilane,3-bromoisropyldiethylcyclohexoxysilane,3-chloropropylcyclopentyldieneethoxysilane,3-bromoisobutyltrimethoxysilane,3-chloroisobutylbis(ethoxyethoxy)methylsilane,4-bromo-n-butyltriethoxysilane,4-chloro-n-butyldiethoxycyclopentylsilane,5-chloro-n-pentyltri-n-butoxysilane, 5-bromo-n-pentyltriethoxysilane,4-bromo-3-methylbutyldimethoxyphenylsilane,5-bromo-n-pentyltri-n-butoxysilane, 5-chloro-n-pentyltriethoxysilane,6-chloro-n-hexylethoxydimethylsilane,6-bromo-n-hexylpropyldipropoxysilane,6-chloro-n-hexyldiethoxyethylsilane, 7-chloro-n-heptyltriethoxysilane,7-chloroheptyldimethoxycycloheptylsilane, 7-bromo-n-heptyl-,diethoxycyclooctylsilane, 8-chloro-n-oxtyltriethoxysilane,8-bromo-n-octyldimethylcyclohexoxysilane,3-chloropropyldiethoxyphenylsilane,3-chloropropylmethoxyethoxybenzylsilane,3-bromopropyldimethoxybenzylsilane and/or the hydrolysis and/or homo-and/or co-condensation products thereof or, judiciously,1,4-chlorophenyltrimethoxysilane, 1,4-chlorobenzyltriethoxysilane andchloromethyl-p-methylphenyltrimethoxysilane and/or the hydrolysis and/orhomo- and/or co-condensation products thereof are used. Particularpreference is given to using pure chloroalkyl-substituted alkoxysilanesin the process of the invention.

With particular advantage, in relation to the haloalkyl group ofcomponent A and to the tertiary nitrogen of component B, components Aand B are used in a molar ratio of 2:1 to 1:100, more particularly of2:1 to 1:10, preferably of 2:1 to 1:5, more preferably of about 1:1 toabout 1:1.5. 1:1, in which case optionally first a ratio of 1:1 is setand subsequently in addition, per portion, about 0.2 of component B inrelation to the component A present is added in 1 to 4 portions.

A process regime which has proven particularly advantageous is one inwhich water is used in an amount of 0.5 to 500 mol per mole of siliconatoms present in component A, preferably in at least one of thehydrolysis steps 0.5 mol of water per mole of hydrolyzable alkoxy groupon the silane of the formula II, in which case in total it is preferredmore particularly to use 0.5 to 25 mol of water, preferably 5 to 25 molof water per mole of silicon atoms in respect of component A used, morepreferably 10 to 25 mol of water per mole of the silicon atoms, moreparticularly 12 to 25 mol of water per mole of silicon atoms.

In this context it is further of advantage if the water, moreparticularly in defined amounts, is metered continuously ordiscontinuously, in portions, into component A, optionally in a mixturewith component B, or into the quaternary-amino alcohol-functional,organosilicon compound of the formula IV

(R¹0)_(3-x-y)(R²)_(n)Si[R³)_(n)CH₂—N⁺[—(CH₂)_(m)OH]_(z)(R⁴)_(3-z)]_(1+y)·(1+y)[Hal⁻]  (IV),

that is formed; preferably the water is added discontinuously withstirring, more preferably in portions, advantageously in 1 to 15portions, more particularly in 2 to 12 portions, where in formula IV R¹,R², R³, R⁴, x, y, z, n and m have the definition defined above, moreparticularly according to claim 2. With further preference, additiontakes place in portions, in each case as a defined amount of water, of0.5 to 4.0 mol of water per mole of silicon atoms, preferably around 1.0to 2.0 mol of water per mole of silicon atoms, more preferably around1.5 mol plus/minus 0.5 mol, and optionally a final portion with 5 to 25mol of water per mole of silicon atoms is added.

Depending on the process regime, it has proven advantageous if thereaction is carried out in the presence of a solvent, more particularlyan alcohol or an alcohol mixture or an alcohol/water mixture, withglycols also being included among the alcohols, preferably in thepresence of the alcohol formed in the hydrolysis of the compound offormula II, more preferably in the presence of ethanol, methanol,n-propanol or isopropanol. In this case, the added solvent is suitablyremoved during the removal from the system of the hydrolysis alcoholformed during the reaction.

The hydrolysis alcohol formed during the reaction is removedsubstantially completely preferably by distillation, more particularlyduring the reaction itself. In accordance with one particularlypreferred process regime, for instance, it is possible for the amount ofhydrolysis alcohol and water, removed by distillation, in the azeotropicmixture to be compensated by additional addition of water.

Volatile solvents, such as an added solvent and/or the alcohol formed byhydrolysis in the reaction, i.e., any groups which can be hydrolyzed tovolatile solvent, more particularly hydrolysis alcohol, are removed downto a level in the overall composition of below 12% by weight to 0% byweight, preferably by distillation in accordance with methods familiarto the skilled person. A composition is considered free from solvents ifthe amount of solvents in the overall composition has been adjusted tobelow 10% by weight to 0% by weight, more preferably below 5% by weight,very preferably below 2% by weight to 0.0001% by weight, moreparticularly 1 to ≦0.5% by weight, preferably 0.5 to ≦0.1% by weight, itbeing possible for the removal of volatile solvent to take place duringthe reaction and/or thereafter by distillation, more particularly underreduced pressure in the range from 0.1 to 1000 mbar, preferably from 80to 300 mbar, more preferably in the range from 80 to 180 mbar. Suitably,however, the pressure may also be lowered from ambient pressure to areduced pressure in the course of the reaction. The distillation maytake place discontinuously or continuously by means of a distillationcolumn, thin-film evaporator and also other apparatus familiar to theskilled person. In the distillation, it is preferred to distill untilonly water is still detectable at the top of the separating column.Water removed by distillation can be supplemented by renewed addition ofwater. At the end of the distillation, the desired final concentrationof the solution can be set by adding further water.

In accordance with the process of the invention, the reaction is carriedout advantageously under a pressure of 1 mbar to 100 bar, preferably atabout 1 mbar to 1.1 bar, more preferably under ambient pressure(atmospheric pressure), and at a temperature of 20 and 150° C.,preferably between 40 to 120° C., more preferably between 60 to 100° C.,more particularly from 80 to 95° C.

Below, preferred process regimes for preparing the compositions aredescribed in more detail, without confining the subject matter of theinvention to these regimes; the skilled person knows of additional,customary process variations.

With regard to the implementation of the processes of the invention ithas proven advantageous if, prior to the reaction ofhaloalkyltrialkoxysilane of the formula II with an amino alcohol of theformula III, more particularly of 3-chloropropyltriethoxysilane (CPTEO)with N,N-dimethylethanolamine, the haloalkyltrialkoxysilane isprehydrolyzed, and hydrolysis alcohol released is removed bydistillation, as shown in example 5, for example, without restrictingthe process to that example. If there is no prehydrolysis ofhaloalkyltrialkoxysilane of the formula II, more particularly of CPTEO,prior to the reaction with the amino alcohol, more particularly withN,N-dimethylethanolamine, then it is advantageous to add the aminoalcohol in excess in order to prevent extensive precipitation of CPTEO,as shown by way of example in example 3, without restricting the processto that example. Where necessary, excess amino alcohol, such asN,N-dimethylethanolamine, can be separated off distillatively. Generallyspeaking, in all processes, a haloalkyltrialkoxysilane of the formulaII, more particularly CPTEO, that has not reacted completely with theamino alcohol of the formula III, such as N,N-dimethylethanolamine, canbe precipitated in principle by addition of water, as in example 2, forexample. Where the reaction of the haloalkyltrialkoxysilane of theformula II, more particularly of CPTEO, takes place with the aminoalcohol of the formula III, such as N,N-dimethylethanolamine, atexcessively high temperatures, as for example at temperatures of 140°C.-150° C., then this can result in intense discolorations of theproduct, as depicted in example 4, for example.

The invention also in particular provides process variants in which

-   a) component A is introduced together with a solvent and a defined    amount of water is added, component B is added, hydrolysis alcohol    formed is removed at least partly from the system, and water is    added in defined amounts, or-   b) component A is introduced and a solvent is added, a defined    amount of water is added, component B is added, hydrolysis alcohol    formed is removed at least partly from the system, and water is    added in defined amounts, or-   c) component A is introduced and a solvent is added, a defined    amount of water is added, hydrolysis alcohol formed is removed at    least partly from the system, thereafter component B is added, and    hydrolysis alcohol formed is removed at least partly from the    system, a defined amount of water is added and hydrolysis alcohol    formed is removed at least partly from the system, and water is    added in defined amounts, or-   d) component A is reacted with component B at elevated temperature,    and further component B is added in a defined amount, and    subsequently a defined amount of water is added, hydrolysis alcohol    formed is removed at least partly from the system, and water is    added in defined amounts, or-   e) component A is introduced and a solvent is added, a defined    amount of water is added, and hydrolysis alcohol formed is removed    at least partly from the system, subsequently component B is added,    and at elevated temperature a defined amount of water is added, and    hydrolysis alcohol formed is removed at least partly from the    system, and optionally water is added in defined amounts, or-   f) component A is introduced together with a solvent and a defined    amount of water is added, hydrolysis alcohol formed is removed at    least partly from the system, component B is added, hydrolysis    alcohol formed is removed at least partly from the system, and water    is added in defined amounts.

Further preference is given to the more specific process regimes, butwithout restricting the invention to them. Particularly preferred,therefore, are processes for preparing the compositions comprisingquaternary-amino alcohol-functional, organosilicon compounds, moreparticularly of quaternary-amino alcohol-functional siloxanols of thecompounds, such as of the idealized formula I, for example, in which

-   a) component A is introduced together with a solvent, more    particularly alcohol, such as ethanol or methanol, and a portion of    a defined amount of water is added, more particularly about 1.5 mol    of water per mole of silicon atoms, component B is added and is    heated, more particularly under reflux, hydrolysis alcohol formed is    removed at least partly under atmospheric pressure from the system,    and water is added in defined amounts in portions, more particularly    about a further 1 to 15 portions with in each case 0.5 to 3 mol,    preferably in each case 1.5 mol of water per mole of silicon atoms,    subsequently the hydrolysis alcohol is removed under reduced    pressure and water is added until the amount of the hydrolysis    alcohol in the overall composition is below 5% by weight; preferably    the hydrolysis alcohol is distilled off and new water is added until    the composition is substantially free from solvent or hydrolysis    alcohol, or-   b) component A is introduced and a solvent is added, more    particularly alcohol, preferably the alcohol formed during the    hydrolysis, as, for example, ethanol or methanol, a portion of a    defined amount of water is added, more particularly about 0.5 to 3.0    mol of water per mole of silicon atoms, preferably in each case 1.5    mol of water per mole of silicon atoms, consequently, preferably,    prehydrolysis takes place, component B is added and the portion is    heated, more particularly under reflux, hydrolysis alcohol formed is    removed at least partly under atmospheric pressure from the system,    preferably completely, and water is added in defined amounts in    portions, more particularly about a further 1 to 15 portions with in    each case 0.5 to 3 mol, preferably in each case 1.5 mol, of water    per mole of silicon atoms, or-   c) component A is introduced and a solvent is added, more    particularly alcohol, preferably the alcohol formed during the    hydrolysis, as for example ethanol or methanol,    -   subsequently a portion of a defined amount of water is added,        more particularly about 0.5 to 3.0 mol of water per mole of        silicon atoms, preferably in each case 1.5 mol of water per mole        of silicon atoms, preferably, therefore, prehydrolysis takes        place, hydrolysis alcohol formed is removed at least partly        under atmospheric pressure from the system after which component        B is added, hydrolysis alcohol formed is optionally removed at        least partly under atmospheric pressure from the system, and the        reaction mixture is heated under reflux, a portion of a defined        amount of water is added, and hydrolysis alcohol formed is        removed at least partly under atmospheric pressure from the        system, and water is added in defined amounts in portions,        preferably completely, and water is added in defined amounts in        portions, more particularly about a further 1 to 15 portions        with in each case 0.5 to 3 mol, preferably in each case 1.5 mol,        of water per mole of silicon atoms, or-   d) component A is reacted with component B at elevated temperature,    and further component B is added in defined amounts discontinuously    or continuously, until component A has reacted substantially    completely with component B, more particularly to form the compound    of the formula IV, thereafter a portion of a defined amount of water    is added, and hydrolysis alcohol formed is removed at least partly    under atmospheric pressure from the system, and water is added in    defined amounts in portions, preferably completely, and water is    added in defined amounts in portions, more particularly about a    further 1 to 15 portions with in each case 0.5 to 3 mol, preferably    in each case 1.5 mol, of water per mole of silicon atoms, or-   e) component A is introduced and a solvent is added, then a portion    of a defined amount of water is added, more particularly about 0.5    to 3.0 mol of water per mole of silicon atoms, preferably in each    case 1.5 mol of water per mole of silicon atoms, preferably,    therefore, prehydrolysis takes place, and hydrolysis alcohol formed    is removed under reduced pressure at least partly from the system,    and subsequently component B is added in defined amounts    discontinuously or continuously, and at elevated temperature at    least one portion of a defined amount of water is added, more    particularly as elucidated above, and hydrolysis alcohol formed is    removed at least partly under atmospheric pressure or under reduced    pressure from the system, and optionally water is added in defined    amounts in portions, more particularly in 1 to 15 portions, as set    out above.

In accordance with one further preferred alternative, the process canalso be carried out by adding optionally a solvent, preferably analcohol, more preferably methanol, ethanol, or isopropanol, to componentA, prehydrolyzing component A with water in an amount of 0.5 to 3.0 molof water per mole of the silicon atoms present, preferably with 0.5 to 2mol of water per silicon atoms present, more preferably around 1.5 molof water per mole of silicon atoms, adding component B, adjusting thereaction mixture present, at ambient pressure or reduced pressure, to atemperature of between 20 and 150° C., preferably around 40 to 120, morepreferably around 60 to 100° C., and removing the hydrolysis alcoholformed at least partly, preferably substantially completely, from thereaction mixture, and also adding the solvent optionally used, and atthe same time optionally water, in defined amount, optionally dilutingthe resultant composition with water, adjusting the solids content inthe composition preferably to 0.1% to 99.9% by weight, and subsequentlyoptionally admixing or contacting the composition with at least onefurther component from the series of pigments, fillers, binders,crosslinkers, optical brighteners, thickeners, rheological auxiliaries,coating auxiliaries or another auxiliary.

In the aforesaid processes it is particularly preferred if thecomposition is adjusted by addition of water to a viscosity of less than1500 mPa s, preferably to a viscosity in the range from 1 to 300 mPa s,more preferably 1 to 100 mPa s, very preferably 5 to 60 mPa s, inaccordance with the invention 5 to 20 mPa s. To the skilled person it isclear that the adjustment of the viscosity may take place in principleduring the preparation and also at a later point in time, as, forexample, prior to use.

The addition of the entire amount of water in one step for the reactionmay lead to the formation of insoluble precipitates, which diminish theyield and which have to be removed by costly and inconvenient filtrationfor the purpose, for example, of producing solutions of the composition.

In the process, advantageously, in accordance with the invention, asilane of the formula II, more particularly a chloroalkyl-functionalsilane optionally the hydrolysis and/or condensation product thereof, ismixed with a tertiary amino alcohol of the formula III, optionally inthe presence of a solvent, and in the presence of 0.5 to 200 mol ofwater per mole of silicon atoms there is a quaternization—on thenitrogen atom with formation of a compound of formula IV and/or I—and atleast partial hydrolysis and optionally condensation (of thealkoxysilanes to silanol groups, followed by a condensation to formSi—O—Si bridges)—of the compounds of the quaternary-aminoalcohol-functional, organosilicon compounds comprising siloxanololigomers. The reaction may be carried out preferably in a kind of“one-pot reaction”, batchwise for example, in which case hydrolysisalcohol is distilled off actually during the reaction and water can besupplemented by metering at substantially the same time. In this case,the pressure in the reaction vessel may also be lowered as the reactiontime goes on; in other words the volatile organic components, moreparticularly the hydrolysis alcohol formed, are removed at leastproportionally from the system by distillation under reduced pressure.

In the process of the invention it is also possible to carry outfiltration, or for a composition obtained in accordance with theinvention to be filtered, as and when required, in a conventional way,if cloudiness occurs.

In accordance with the invention, the reaction can be carried outwithout additional catalyst. It may, however, prove useful to add ahydrolysis and/or condensation catalyst as for example—but notexclusively—an organic or inorganic acid, such as formic acid, aceticacid, propionic acid, citric acid, hydrogen chloride, as a gas,concentrated or aqueous hydrochloric acid, boric acid, nitric acid,sulfuric acid, phosphoric acid, to name but a few. Correspondingly it isalso possible at any time to add an organic or inorganic acid in orderto set the pH of the composition or reaction mixture.

Furthermore, it may be preferable, as a further component in the processof the invention, to use metal oxides, preferably metal oxides havinghydroxyl groups capable of condensation. These oxides are moreparticularly silica, fumed silica, precipitated silica, silicates, boricacid, titanium dioxide, aluminum oxide, aluminum oxide hydrate, ATH(aluminum trihydroxide, Al(OH)₃), magnesium hydroxide (Mg(OH)₂), ceriumoxide, yttrium oxide, calcium oxide, iron oxides, zirconium oxide,hafnium oxide, boron oxide, gallium oxide, indium oxide, tin oxide,germanium oxide, and also corresponding hydroxides and oxide hydrates,and also mixtures of at least two of the aforementioned compounds withone another.

Volatile solvents or groups hydrolyzable to volatile solvents areconsidered to encompass alcohols, such as methanol, ethanol,isopropanol, n-propanol, and alkoxy groups, which hydrolyze to formalcohols, radicals containing acyloxy groups, and also the acetic acidor formic acid derived by hydrolysis, or else aryloxy groups, which mayform phenols, and also glycols, and also partially etherified glycolssuch as ethylene glycol, diethylene glycol or methoxyethanol, whicheither are added to the formulation or are formed by hydrolysis of theirsilyl esters.

In the context of the invention, condensation products are understood tobe both homo- and co-condensation products from the reaction ofhydrolyzed alkoxysilanes, oligomeric or else polymeric organosiliconcompounds containing Si—OH groups, and also condensation products withthe participation of block co-condensates, of the initially in each casehydrolyzed and condensed compounds of the formulae II and IV, whichsubsequently as well may be reacted with amino alcohols to formcompletely quaternized block co-condensates.

The invention accordingly also provides a quaternary-aminoalcohol-functional, organosilicon compound of the formula IV, as per thedefinition above for R¹, R², R³, R⁴, Hal, x, y, z, n and m of theformula IV or as per claim 1, more particularly as an intermediate forpreparing the quaternary-amino alcohol-functional siloxanol oligomershown in idealized form as formula I

(R¹0)_(3-x-y)(R²)_(n)Si[R³)_(n)CH₂—N⁺[—(CH₂)_(m)OH]_(z)(R⁴)_(3-z)]_(1+y)·(1+y)[Hal⁻]  (IV),

Likewise provided by the invention is a process for preparing aquaternary-amino alcohol-functional, organosilicon compound of theformula IV

(R¹0)_(3-x-y)(R²)_(n)Si[R³)_(n)CH₂—N⁺[—(CH₂)_(m)OH]_(z)(R⁴)_(3-z)]_(1+y)·(1+y)[Hal⁻]  (IV),

by reacting the haloalkyl-functional silane of the formula II, asdefined above or as in claim 2, with an amino alcohol of the formulaIII, as defined above or as in claim 2, to give a compound of theformula IV, as defined above or as in claim 1. More particularly, it ispossible to react a silane of the formula II with a silane of theformula III at an elevated temperature, optionally in the presence of apreferably inert solvent, and further silane is added in definedamounts, discontinuously or continuously, until the silane of theformula II has undergone substantially complete reaction with the aminoalcohol of the formula III. Working up may take place in accordance withthe methods and techniques customary to the skilled person, such as, forexample, distillation, optionally with a thin-film evaporator.

The invention accordingly further provides as well a compositioncomprising quaternary-amino alcohol-functional, organosilicon compounds,more particularly quaternary-amino alcohol-functional siloxanololigomers, as in accordance with the idealized formula I, and compoundsof the formula IV, and water, said composition being obtainable by oneof the above-elucidated processes or by a process as claimed in any ofclaims 2 to 14 or 16. In this context it is particularly preferred ifthe quaternary-amino alcohol-functional, organosilicon compoundsobtainable in the process are water-soluble, including more particularlythe siloxanol oligomers.

The compositions of the invention are distinguished advantageously by alow viscosity in conjunction with high solids content, as demonstratedby the working examples. This combination of low viscosity and highsolids content is a necessary prerequisite for a high capacity in theproduction of coatings. At the same time, the compositions of theinvention are substantially VOC-free. Accordingly, the compositions ofthe invention exhibit significantly enhanced performance relative toknown compositions. Compositions comprising alcohol, however, are notthereby fundamentally ruled out.

The composition obtained in accordance with the invention is generallyliquid and of low to moderate viscosity, with the viscosity moreparticularly being below 1500 mPa s to 0.001 mPa s, preferably between1000 and 1 mPa s, more preferably below 300 mPa s, preferably below 200mPa s, more preferably below 100 mPa s, better still between 100 mPa sand 1 mPa s; further preference is given to ranges from 50 to 1 mPa s,more particularly from 20 and 5 mPa s (the viscosity is determined inaccordance with DIN 53015).

It is further preferred if the compositions have a solids content in thecomposition of 0.1% to 99.9% by weight, preferably 0.5 to 90% by weight,more particularly of 5% to 70% by weight, preferably of 7% to 60% byweight, more preferably of 30% to 60% by weight, with all theconstituents in the composition making 100% by weight in total.

It is particularly preferred here if the compositions have a solidscontent preferably of 7% to 60% by weight, more preferably of 30% to 60%by weight, preferably of 40% to 60% by weight and the composition at thesame time has a viscosity of <1500 mPa s, preferably ≦1000 mPa s, morepreferably 1 to 300 mPa s, more particularly of 1 to 100 mPa s, betterstill of 5 to 20 mPa s. One particularly preferred composition has asolids content of 30% to 60% by weight with a viscosity of 5 to 20 mPas. Compositions of the invention have a solids content of 40% to 60% byweight, at viscosity of 5 to 20 mPa s.

A composition is preferred, moreover, when it has a total nitrogencontent of 0.1% to 15% by weight, more particularly of 1.0% to 4.0% byweight with a viscosity of 1 to 100 mPa s, more preferably 5 to 20 mPas, and optionally a pH in the range from 5.0 to 11.0, preferably from6.0 to 9.0.

A composition may be further preferred if it additionally oralternatively has a water content of 0.0999 to 99.9% by weight and avolatile solvent/hydrolysis alcohol content in the overall compositionof below 12% by weight to 0% by weight, preferably below 1 to 0.0001% byweight, with all of the constituents in the composition making 100% byweight in total.

It may be preferable, furthermore, if a composition comprises at leastone other of the following components from the series pigments, fillers,binders, crosslinkers, optical brighteners, coating auxiliaries or otherauxiliaries.

In accordance with the invention the present composition issubstantially free from volatile solvents, preferably from hydrolysisalcohol, and more particularly, on crosslinking, no longer releases anyhydrolysis alcohol, and more particularly it has a flash point of above90° C.

The claimed compositions are substantially stable in storage. That is,they do not exhibit any visible changes such as cloudiness orsedimentation or gelling within two weeks, preferably 3 months, morepreferably 1 year.

Prior to use, the compositions of the invention and also the endproducts of the invention can as and when necessary be dilutedadvantageously to a content of between 10% to 0.01% by weight,preferably to 5% to 0.1% by weight, with water or other solvents or elsemixtures thereof.

The invention also provides a formulation comprising a composition ofthe invention, more particularly aqueous composition, which furthercomprises at least one of the following components from the seriespigments, binders, crosslinkers, optical brighteners, coatingauxiliaries, active ingredient and/or auxiliary and/or filler.

The compositions of the invention can also be used with very goodsuitability in inkjet coatings, more particularly for high gloss coatson paper.

Likewise provided by the invention is the use of the quaternary-aminoalcohol-functional, organosilicon compound or of a composition, moreparticularly as claimed in any of claims 1 to 20, for modification,treatment and/or production of formulations, substrates, articles,organic or inorganic materials, composite materials, papercoating slips,inkjet applications, preferably for producing inkjet photographicpapers, papercoating materials, paper, textiles, fillers, biocidally,fungicidally and/or virucidally acting formulations, biocidally,fungicidally and/or virucidally acting coatings, for finishing of fibermaterials, yarns and/or textiles, for textile impregnation, forantistaticization of surfaces, more particularly of sheetlike, fibrous,woven, granular and/or pulverulent materials, hence more particularlyfor the cationic modification of inorganic or polar organic surfaces, asfor example fillers, pigments, glass, mineral, and ceramic surfaces,natural and synthetic polar substances, such as, for example,polyesters, polyamides, wool, silk, cellulose, lignocellulose, wood,proteins, sugars, polysaccharides, and the like, which may also bepresent in particulate form or fiber form, in the cm, mm, micronized orelse nanometer range.

One preferred application for the compositions of the invention is theproduction of papercoating slips. For this purpose it is suitable firstto prepare an aqueous silica dispersion and to treat it with the silanesystem of the invention, usually under high shearing forces appliedusing dispersing equipment customary in the industry. For optimumresults, a mean aggregate size of 140-160 nm is desirable. Within asystem, higher degrees of filling lead in the course of dispersing to adecrease in the average particle size. The resulting silanized silicadispersion is notable advantageously for a high solids content, highstability in storage, and low sedimentation tendency. Preferably, in asecond step, the papercoating slip is prepared from the silanized silicadispersion by addition of binder, preferably polyvinyl alcohol, and ofcrosslinker, preferably boric acid, and is especially suitable forproducing photographic inkjet papers.

The lower the solids content of the formulation, the lower the capacityof the coating lines operated with it, because the volatile constituentsof the papercoating compositions (mainly water here) generally have tobe removed thermally. The higher the solids content of the formulation,the lower the amount of water which has to be removed and the higher therate of speed at which the coating lines can be operated. A solidscontent of >20% by weight, preferably greater than 24% by weight, isdesired for papercoating compositions under the conditions selected inexample S4. A description of this application can be found in detail inthe parallel DE application with the title “Process for preparing adispersion comprising silicon dioxide particles and cationizing agent”.

The composition of the invention can be employed by applying it to asubstrate, generally by dipping, spreading, rubbing, spraying, moreparticularly with droplet sizes below 200 μm, preferably less than 100μm down into the nanometer range; depositing, spincoating, using curtaincoaters, or any other techniques known to the skilled person. To thisend, the composition is adjusted to an organosilicon compoundconcentration suitable for the method employed. Depending on theprocessing method, therefore, the concentration may range from 0.01% byweight of organosilicon compound to 99.5% by weight in the composition.The methods of application are well known to a person skilled in thepertinent art. In addition, a coating applied to a substrate can cure orbind to the substrate in a conventional manner under ambient conditionsand/or via an additionally thermal and/or photochemical treatment. Inthis way, for example, a composition of the invention can be used totreat organic or inorganic substrates or as an input component informulations.

The examples below illustrate the present invention, more particularlythe process of the invention and also the compositions of the invention,in more detail, without restricting the invention to these examples.

EXAMPLES Methods of Determination:

Hydrolyzable chloride was titrated potentiographically with silvernitrate (for example, Metrohm, type 682 silver rod as indicatorelectrode and Ag/AgCl reference electrode or another suitable referenceelectrode). Total chloride content after Wurtzschmitt digestion. Forthis purpose, the sample is digested with sodium peroxide in aWurtzschmitt bomb. After acidification with nitric acid, chloride ismeasured potentiographically with silver nitrate, as above.

In the case of a complete reaction of the chloroalkyl functionality withtertiary amines, the analytical values for hydrolyzable chloride andtotal chloride are identical and are therefore a measure of thecompleteness of the reaction, since the sum total of saltlike chloride(amine hydrochloride) and covalently bonded chlorine (chloroalkylfunctionality) is determined by total chloride, and exclusively saltlikechloride or chloride which can be eliminated with water (aminehydrochloride in the present case) is determined by hydrolyzablechloride. At the beginning of the reaction, the value for hydrolyzablechloride is zero and increases at complete conversion to the value whichis measured for total chloride. Therefore, these analyses are veryuseful in addition to ¹H and ¹³C NMR spectroscopy for reactionmonitoring.

The alcohol content after hydrolysis is determined by gaschromatography. For this purpose, a sample of a defined amount ishydrolyzed with sulfuric acid (5 g of sample, 25 ml of H₂SO₄, w=20%). 75ml of distilled water are added. Thereafter, neutralization takes placewith aqueous sodium hydroxide solution, and a steam distillation isperformed. Internal standard: 2-butanol.

Determination of nitrogen, organically bound, ammonium, etc. organicallybound nitrogen can be converted into ammonium by means of Kjeldahldigestion and determined acidimetrically as ammonia following additionof aqueous sodium hydroxide solution. Method: up to 5 g of sample areheated with 10 ml of sulfuric acid (concentrated) and a Kjeldahl tablet(Merck 1.15348) until the digestion solution is pale and clear apartfrom any precipitated silica. The digestion vessel is attached to adistillation apparatus, and ammonia released as a result of addition ofaqueous sodium hydroxide solution (27%) is distilled over into thereceiver. With addition of boric acid (2%), the ammonia content istitrated with sulfuric acid (c(H₂SO₄)=0.05 mol/l or 0.005 mol/l).V=consumption of sulfuric acid in ml, c=concentration of sulfuric acidin mol/l, z=number of equivalents of sulfuric acid=2, E=initial mass inmg.

${{Evaluation}:{N\mspace{14mu}\lbrack\%\rbrack}} = \frac{100 \cdot V \cdot c \cdot z \cdot 14.01}{E}$

Determination of S10₂ takes place following decomposition using sulfuricacid and Kjeldahl catalyst, by determining the weight of theprecipitated SiO₂.

Method: The 1 g sample is placed in a 250 ml glass beaker and a Kjeldahltablet (e.g., Merck #15348) and 20 ml of sulfuric acid (concentrated)are added. The solution is slowly heated. The organic constituents areoxidized, until the digestion solution, with fuming of the sulfuricacid, remains clear and pale. After cooling and after cautious dilutionto approximately 200 ml, the precipitated silica is removed byfiltration on a white ribbon filter. The filter is washed with wateruntil the pH of the wash water is >4, and then dried and incinerated ina platinum crucible. The residue is ignited at 800° C. and reweighed.After fuming with hydrofluoric acid (concentrated), ignition at 800° C.and reweighing are repeated. m=weight difference before and afterfluorination in g; E=initial mass in g.

${{Evaluation}:{{SiO}_{2}\mspace{11mu}\lbrack\%\rbrack}} = \frac{100 \cdot m}{E}$

Shown below are the DIN standards used in determining the statedparameters:

Solids content: DIN 38409-1 (1987-01-00)Refractive index: DIN 51423 (2010-02-00)

Density: DIN 51757 (1994-04-00) Viscosity DIN 53015 (2001-02-00)

Color number DIN EN ISO 6271 (2005-03-00)

Cloudiness DIN EN ISO 7027 (2000-04-00) Example 13-Chloropropyltriethoxysilane (CPTEO)/N,N-dimethylethanolamineApparatus:

4 l stirred reactor with distilling device, pot thermometer, topthermometer, vacuum pump, manometer metering device, and pressure filter

Materials used m n w (input) (inputs) (inputs) Inputs [g] [mol] [%]Comment CPTEO 1283.0 5.328 28.79 M = 240.8 g/mol, bp = 230° C. N,N-570.5 6.400 12.80 M = 116.21 g/mol Dimethylethanolamine bp = 133° C.Ethanol 160.0 3.59 Deionized water: 1^(st) addition 143.9 7.992 3.232^(nd) addition 143.9 3.23 3^(rd) addition 143.9 3.23 4^(th) addition144.5 3.24 5^(th)-12^(th) addition 1866.1 41.88 Σ (inputs) 4455.8 100.00m (Ethanol from hydrolysis) = 735.3 gFinal mass of product: 2438.5 g (theory: 2562.7 g)Final mass of distillate: 2236.0 g

Procedure: 1. Hydrolysis

A 4 l four-neck flask was charged with 1283.0 g of CPTEO (5.328 mol) and160.0 g of ethanol. At RT, 143.9 g of deionized water (1.5 mol H₂O/molSi) were added dropwise over the course of 16 minutes. During thisaddition, the pot temperature rose to around 40° C.

2. Quaternization Reaction

Subsequently 570.5 g (6.400 mol) of dimethylethanolamine were stirred inover the course of 6 minutes. During this addition, the pot temperaturerose from 40° C. to around 48° C. This was followed by boiling at refluxfor around 45 minutes (pot temperature around 85° C.).

3. Distillation at RT/Quaternization Reaction

Under atmospheric pressure, 1706.6 g ofwater/ethanol/dimethylethanoldiamine were distilled off over the courseof around 6 hours. During this time, 2038.3 g of water were stirred inin seven portions. After distillation for around 3 hours, a total of432.4 g of deionized water were introduced in three portions (2^(nd) to4^(th) water addition). A sample of the pot then showed itself to bereadily soluble in deionized water.

3. Distillation Under Reduced Pressure

Over the course of 1.7 hours, at a pot temperature of 50 to 55° C. andunder an absolute pressure of around 140 mbar, 529.4 g ofwater/ethanol/dimethylethanol-diamine mixture were distilled off. At theend of the distillation, 560.17 g of deionized water were stirred in.This gave a slightly cloudly/slightly yellowish liquid of low viscosity.Yield: 2521.7 g

4. Filtration

Filtration was carried out in a 2 l laboratory pressure filter at RTwith an overpressure of around 0.5 bar of N2. The filter used was acut-to-size filter plate (pilot plant, used for bubble filters) having adiameter of 135 mm. The filtration time was around 20 minutes.Filtration produced a clear, slightly yellowish liquid of low viscosity.

Analysis (Product):

Determination Unit Result Method Total N wt % 2.9 see above Totalchloride wt % 7.4 see above Hydrolyzable chloride wt % 7.0 see aboveSiO₂ wt % 12.5 see above Solids content wt % 47.5 DIN 38409-H1-1 Ethanol(after hydrolysis) wt % <0.1 see above pH 8.6 Refractive index (20° C.)1.4146 DIN 51423 Density (20° C.) g/cm³ 1.126 DIN 51757 Viscosity (20°C.) mPa s 12.3 DIN 53015 Flash point ° C. >95 DIN EN ISO 2719 Colornumber mg Pt—Co/l 55 ISO 6271 Turbidity TU/F 0.36 ISO 7027 ¹H and ¹³CNMR: Purity of the target compound around 95.8 mol %. 4.2 mol % of freedimethylethanol-amine. No indications of any transesterification of theaminoethanol group to form SiOR. ²⁹Si NMR: 1% Si silane 7% Si M 45% Si D47% Si T structures

The new product is notable for even better processing and applicationsproperties in the production of high-gloss inkjet photographic papers.

Comments on the Reaction of N,N-dimethylethanolamine with CPTEO

Differences in the process for the reaction of haloalkylalkoxysilaneswith tertiary amines, as in PCT/EP2010/053626.

-   -   As set out in example 5, it proves advantageous if the CPTEO is        prehydrolyzed prior to the reaction of CPTEO with        N,N-dimethylethanolamine, and the hydrolysis alcohol released is        removed by distillation.    -   If there is no prehydrolysis of CPTEO prior to reaction with        N,N-dimethylethanol-amine, then it proves advantageous to        operate with an excess of N,N-dimethyl-ethanolamine, in order to        prevent significant precipitation of CPTEO (see example 3). If        necessary, excess N,N-dimethylethanolamine can be separated off        by distillation.        -   Incompletely reacted CPTEO with N,N-dimethylethanolamine can            be precipitated in principle by addition of water (see            example 2).        -   If the reaction of CPTEO with N,N-dimethylethanolamine is            carried out at temperatures of 140 to 150° C., this leads to            intense discoloration of the product (see example 4).

Example 2

A 500 ml four-neck flask was charged with 160.01 g of Dynasylan® CPTEO(0.664 mol). At RT, 20.73 g of ethanol were stirred in and then 18.09 gof deionized water (1.5 mol H₂O/mol Si) were added dropwise withstirring over the course of 13 minutes. During this addition, the pottemperature rose from 20° C. to 33° C. Subsequently, over the course oftwo minutes, 59.34 g of N,N-dimethylethanolamine (0.665 mol) werestirred in, leading to an increase in the pot temperature to 42° C. Thiswas followed by boiling under reflux at a pot temperature of around 87°C. for one hour. Thereafter, ethanol mixture was distilled off underatmospheric pressure. In the course of the distillation, the pottemperature reached a maximum temperature of 107° C. 46 minutes afterthe beginning of distillation, 36.08 g of deionized water were meteredin over the course of three minutes. A further 184.88 g of deionizedwater were added during further distillation. A total of 184.5 g ofliquid were removed by distillation. After a total of 7.5 hours, thebatch was cooled to RT. The yield was 266.07 g (corresponding to 90.3%of theory) of clear, slightly yellowish liquid of low viscosity.Deposited on the stirrer were significant quantities of a gel-likesubstance (condensed silane hydrolysate), which was responsible for therelatively low yield (reduced yield as a result of gel deposits).

Analysis:

Determination Unit Result Method Total N wt % 3.0 see above Totalchloride wt % 7.7 see above Hydrolyzable chloride wt % 7.6 see aboveSolids content wt % 51.5 DIN 38409-H1-1 Ethanol (after wt % 0.1 seeabove hydrolysis) pH 7.5 Refractive index (20° C.) 1.4180 DIN 51423Density (20° C.) g/cm³ 1.132 DIN 51757 Viscosity (20° C.) mPa s 14.2 DIN53015 Color number mg Pt—Co/l 30 ISO 6271 Turbidity TU/F 0.23 ISO 7027¹H and ¹³C NMR: 98.2 mol % purity of the quaternary target compound,about 1.8 mol % of free dimethylethanolamine ²⁹Si NMR: 1% Si silane 7%Si M 47% Si D 45% Si T structures

Example 3 20 mol % DMEA Excess, no Gel Deposits

A 500 ml four-neck flask was charged with 160.55 g of Dynasylan® CPTEO(0.667 mol). At RT, 20.12 g of ethanol were stirred in and then 18.05 gof deionized water (1.5 mol H₂O/mol Si) were added dropwise withstirring over the course of 13 minutes. During this addition, the pottemperature rose from 21° C. to 28° C. 33.1 g of hydrolysis ethanol weredistilled off under reduced pressure (140 to 94 mbar absolute pressure)at a pot temperature of around 35° C. over the course of 45 minutes.Subsequently, over the course of four minutes, 71.34 g ofN,N-dimethylethanolamine (0.800 mol) were stirred in, leading to anincrease in the pot temperature to 35° C. Thereafter, 80.08 g of ethanolmixture were distilled off over the course of 38 minutes underatmospheric pressure. Boiling under reflux was carried out for 20minutes at a pot temperature of 96.0 to 92.2° C. Subsequently, 17.99 gof deionized water were metered in over the course of two minutes. Afurther 245.47 g of deionized water were added during furtherdistillation. A total of 232.5 g of liquid were removed by distillation.After a total of 7.65 hours, the batch was cooled to RT. The yield was325.9 g (corresponding to 96.0% of theory) of clear, slightly yellowishliquid of low viscosity. No gel deposits in the reaction vessel.

Analysis:

Determination Unit Result Method Total N wt % 2.7 see above Totalchloride wt % 7.2 see above Hydrolyzable chloride wt % 7.0 see aboveSolids content wt % 47.2 DIN 38409-H1-1 Ethanol (after wt % <0.1 seeabove hydrolysis) pH 8.0 Refractive index (20° C.) 1.4121 DIN 51423Density (20° C.) g/cm³ 1.122 DIN 51757 Viscosity (20° C.) mPa s 10.9 DIN53015 Color number mg Pt—Co/l 25 ISO 6271 Turbidity TU/F 1.0 ISO 7027 ¹Hand ¹³C NMR: 97.3 mol % purity of the quaternary target compound, about2.7 mol % of free dimethylethanolamine ²⁹Si NMR: -% Si silane 6% Si M47% Si D 47% Si T structures

Example 4 CPTEO/N,N-dimethylethanolamine (DMAE) Reaction at 140 to 150°C.

A 500 ml four-neck flask was charged with 160.10 g of CPTEO (0.665 mol).At a pot temperature of 20° C., 59.35 g of N,N-dimethylethanolamine(0.666 mol) were stirred in. At a pot temperature of 140.6 to 151.8° C.,stirring was carried out for 6.8 hours. After a reaction time of around2.5 hours, GC analysis still indicated 14.0 area % of CPTEO and <0.1area % of N,N-dimethylethanolamine in the pot. The pot contents had inthe meantime undergone a change in color from slightly yellowish throughorange to red. After a reaction time of 3.7 hours, GC analysis of thepot sample indicated a CPTEO content of 16.8 area %. At this point 13.98g of N,N-dimethyl-ethanolamine (0.157 mol) were metered in. The potcontents changed color to brown. After a reaction time of a further 22minutes, the GC analysis of the pot contents still indicated 7.4 area %of CPTEO. A further 13.99 g of N,N-dimethylethanolamine (0.157 mol) weremetered in. After a reaction time of a further 13 minutes, GC analysisstill indicated 3.2 area % of CPTEO in the pot contents. 127.55 g ofdeionized water were then metered in over the course of 31 minutes.After a total of 8 hours, the batch was cooled to RT. The pot contentswere virtually clear and brown. The next day, free ethanol was distilledoff under reduced pressure (300 mbar to 176 mbar absolute pressure) at apot temperature of 61.1 to 76.9° C. In total, over around 4 hours,230.28 g of liquid were removed by distillation. During thedistillation, 223.8 g of deionized water were metered in. The yield was348.19 g (corresponding to 95.4% of theory) of clear brown liquid of lowviscosity. No gel deposits in the reaction vessel.

Analysis:

Determination Unit Result Method Total N wt % 3.1 see above Totalchloride wt % 6.6 see above Hydrolyzable chloride wt % 6.3 see aboveSolids content wt % 45.7 DIN 38409-H1-1 Ethanol (after wt % <0.1 seeabove hydrolysis) pH 9.5 Refractive index (20° C.) 1.1429 DIN 51423Density (20° C.) g/cm³ 1.145 DIN 51757 Viscosity (20° C.) mPa s 11.1 DIN53015 Color number Gardner 8 ISO 6271 Turbidity TU/F 1.6 ISO 7027

Example 5

CPTEO/DMAE 1:1 (mol), CPTEO Prehydrolyzed with 1.5 mol of H₂O/mol of Si

A 4 l three-neck flask was charged with 829.30 g of CPTEO (3.444 mol)and 100.40 g of ethanol were stirred in at a pot temperature of 22° C.Subsequently, at room temperature and with intense stirring, 93.12 g ofdeionized water were metered in over the course of 8 minutes. Duringthis addition, the pot temperature rose to 47° C. Under reducedpressure, the hydrolysis ethanol was then distilled off until the pottemperature was 62.2° C. and the absolute pressure was <1 mbar.Subsequently, 307.12 g (3.445 mol) of N,N-dimethylethanolamine werestirred in. During this addition, the pot temperature rose to a maximumof 58.5° C. The pot contents were subsequently heated to 109.4° C., and93.05 g of water were metered in cautiously over the course of 11minutes. After 12 minutes there was a further addition of water (92.75 gin 6 minutes). Distillative removal of ethanol was commenced, underatmospheric pressure. Subsequently more deionized water, in two portions(92.99 g and 93.01 g), was metered in, and then, under reduced pressure,residual free ethanol was distilled off. During the vacuum distillationand after the end of the distillation, a total of a further 956.36 g ofdeionized water were stirred into the reaction mixture. This gave 1773.2g (97.0%) of slightly cloudy/yellowish liquid of low viscosity.

Analysis:

Determination Unit Result Method Total N wt % 2.6 see above Totalchloride wt % 6.8 see above Hydrolyzable chloride wt % 6.5 see aboveSolids content wt % 43.9 DIN 38409-H1-1 Ethanol (after wt % <0.1 seeabove hydrolysis) pH 6.3 Refractive index (20° C.) 1.4059 DIN 51423Density (20° C.) g/cm³ 1.115 DIN 51757 Viscosity (20° C.) mPa s 8.7 DIN53015 Color number mgPt—Co/l 60 ISO 6271 Turbidity TU/F 2.7 ISO 7027

Comparative Example for the Preparation of Dispersions:

Quaternary silane system (CPTEO/TMEDA), prepared from3-chloropropyltriethoxy-silane (CPTEO) and tetramethylethylenediamine(TMEDA).

Comparative Example 1

Water-based, VOC-free solution of a quaternary silane system, preparedfrom 3-chloropropyltriethoxysilane (CPTEO) andtetramethylethylenediamine (TMEDA).

Apparatus: Stirred reactor with distilling device, pot thermometer, topthermometer, vacuum pump, manometer, and metering device

Materials Used:

M N w (input) (inputs) (inputs) Inputs [g] [mol] [%] CommentChloropropyltriethoxysilane 3206.2 13.31 37.3 M = 240.8 g/molN,N,N′,N′-Tetramethyl- 1547.2 13.31 18.0 M = 116.21 ethylenediamineg/mol Deionized water: 1. Addition 1603.1 18.6 2. Addition 641.3 7.5 3.Addition 1600.0 18.6 Σ (inputs) 8597.8 m (ethanol from hydrolysis) =1836.8 g; final mass of product after filtration: 6521.4 g (theory:6761.1 g); final mass of distillate: 2946.5 g

Procedure:

1. Reaction (duration about 9.7 h): chloropropyltriethoxysilane wasintroduced initially and tetarmethylethylenediamine was added rapidlywith stirring. This was followed by the 1^(st) addition of water withinaround 20 minutes (volume flow rate around 4.8 l/h) under vigorousstirring. The pot contents were at this point distingly cloudy, and wereheated under reflux (around 87° C.) for 6 hours. The 2^(nd) addition ofwater was made over the course of 10 minutes to the now clarified potcontents (volume flow rate around 3.9 l/h). After a further 1.5 hours ofheating under reflux, the 3^(rd) addition of water was made withstirring (over the course of around 20 minutes, volume flow rate around4.8 l/h).2. Distillation (duration about 9 h): At a pot temperature of 49° C. to54° C., hydrolysis ethanol was distilled off under reduced pressure(100-270 mbar). Following distillative removal of around 1700 g ofethanol/water mixture, 327 g of water were rapidly added. In order toremove the hydrolysis alcohol by distillation almost to completion, itwas necessary to remove an at least 60% excess (based on the mass ofhydrolysis ethanol) by distillation. The amount of water removed bydistillation was returned at the end of the distillation.3. Filtration (duration around 1 h): Thereafter, the yellowish, slightlycloudy product was filtered via pressure filter (2 l) and Seitz 500depth filter at an overpressure of 0.8 bar (filtration performance atd_(filter)=14 cm: 18 l/h). A clear, slightly yellowish liquid wasobtained.

Analyses:

Determination Result Theory Method Viscosity (20° C.) 70 DIN 53015 [mPas] Density (20° C.) 1.107 DIN 51757 [g/ml] Refractive index 1.4224 DIN51423 (20° C.) Color [mg Pt—Co/l] 75 Solids [%] 48.4 DIN 38409-1 pH 8.61:1 in Wasser, DIN 38404-C5 SiO₂ [%] 11.8 11.8 see above Ethanol after0.5 see above hydrolysis [%] Total N [%] 5.0 5.5 see above Totalchloride [%] 7.2 7.0 see above Hydrolyzable 7.1 7.0 see above chloride[%] NMR: ¹³C NMR: around 15% of the TMEDA groups were present in theform of the bis adduct. Per 100 SiCH₂ groups there was 8 mol % of freeTMEDA. ²⁹Si NMR: 2.5 Si-% silane; 14.6 Si-% M structures; 49.7 Si-% Dstructures; 33.3 Si-% T structures

Preparation of Dispersions

Dispersion examples D1 to D4 below were developed with the proviso thatthe dispersions should be able to be applied in low-viscosity form andshould have similar performance in papercoating in respect of porestructure and pore volume. The measure which emerged for the porosity ofthe coating was the average aggregate size in the dispersion, measuredby dynamic light scattering. For optimum results, an average aggregatesize of 140 to 160 nm was desirable. Within a system, higher degrees offill during dispersing resulted in a decrease in the average particlesize. The examples show that by using the silane system of the inventionit is possible to realize very high levels of fill while at the sametime retaining the desired aggregate size.

Example D1

Dispersion based on fumed silica with a specific surface area of 300m2/g and poly-diallyldimethylammonium chloride (p-DADMAC) (comparativeexample)

1350 g of deionized water were admixed with 60 g of p-DADMAC. Then 320 gof fumed silica were incorporated with stirring by means of a dissolverat 1500 to 4000 rpm, followed by further preliminary dispersing over aperiod of 5 minutes at 2000 rpm. Dispersion then continued with cooling(<30° C.) for ten minutes, now using a rotor-stator dispersing apparatusat 15 000 rpm. To conclude, the dispersion was filtered through a 500 μmsieve.

Example D2

Dispersion based on fumed silica with a specific surface area of 300m2/g and N-butylaminopropyltrimethoxysilane (comparative example)

1200 g of deionized water were admixed with 425 g of fumed silica,incorporated by stirring by means of a dissolver at 1500 to 4000 rpm,followed subsequently by further predispersing over a period of 5minutes at 2000 rpm. Dispersion then continued with cooling (<30° C.)for ten minutes, now using a rotor-stator dispersing apparatus at 15 000rpm. Stirring was then carried out again with the dissolver at 2000 rpm,and a mixture of 21.3 g of N-butylaminopropyltrimethoxysilane, 67 g ofmethanol, and 20 g of formic acid (50 percent strength solution inwater) was added, followed by final dispersion for 60 minutes in therotor-stator system at 5000 rpm at 60° C. To conclude, the dispersionwas cooled and filtered through a 500 μm sieve.

Example D3

Dispersion based on fumed silica with a specific surface area of 300m2/g and quaternary silane system (CPTEO/TMEDA),

Comparative Example

509 g of fumed silica were incorporated by stirring with a dissolver at1500 to 5000 rpm into a mixture of 1215 g of deionized water, 53.0 g ofquaternary silane system (CPTEO/TMEDA system from comparative example1), and 23.4 g of acetic acid (25 percent strength by weight solution inwater), and dispersing was continued at 2000 rpm for 5 minutes. This wasfollowed by final dispersing with a rotor-stator dispersing apparatus(Kinematica Polytron PT6100) over a period of 30 minutes at 10 000 rpm.To conclude, the dispersion was cooled and filtered through a 500 μmsieve.

Example D4

Inventive dispersion based on fumed silica with a specific surface areaof 300 m2/g and the solution from example 1

428 g of fumed silica were incorporated by stirring with a dissolver at1500 to 5000 rpm into a mixture of 805 g of deionized water and 47.4 gof the solution from example 1, and dispersing was continued at 2000 rpmfor 10 minutes. This was followed by dispersing with a rotor-statordispersing apparatus (Kinematica Polytron PT6100) over a period of 30minutes at 10 000 rpm. To conclude, the dispersion was filtered througha 500 μm sieve.

TABLE Physicochemical data of dispersions D1 to D4 Comparison InventionD1 D2 D3 D4 Solids content*⁾ % by wt. 20.0 25.0 30.0 35.0 Particlediameter**⁾ nm 157 154 156 148 Viscosity***⁾ mPa s 47 80 122 142 *⁾afterdrying to constant weight at 125° C.; **⁾by dynamic light scattering(Horiba LB-500); ***⁾at 1000 1/s; 23° C.;

Dispersion examples D5 to D8 showed the maximum solids content possiblewith the respective cationizing additive, independently of the parameterof aggregate size. As expected, the dispersions had very highviscosities, but were still liquid and processable. On account of thesmall particle sizes, further processing to papercoating slips andinkjet papers was not undertaken.

Example D5

Dispersion based on fumed silica with a specific surface area of 300m2/g and poly-diallyldimethylammonium chloride (p-DADMAC) (comparativeexample)

1190 g of deionized water were admixed with 60 g of p-DADMAC. Then 320 gof fumed silica were incorporated with stirring by means of a dissolverat 1500 to 4000 rpm, followed by further preliminary dispersing over aperiod of 5 minutes at 2000 rpm. Dispersion then continued with cooling(<30° C.) for ten minutes, now using a rotor-stator dispersing apparatusat 15 000 rpm. To conclude, the dispersion was filtered through a 500 μmsieve.

Example D6

Dispersion based on fumed silica with a specific surface area of 300m2/g and N-butylaminopropyltrimethoxysilane (comparative example)

1035 g of water were introduced and 21.2 g ofN-butylaminopropyltrimethoxysilane were stirred into the water. After ahydrolysis time of 30 minutes, the initial solution was adjusted to a pHof 4.2 using 63.7 g of acetic acid (25 percent strength by weightsolution in water). Then 423.9 g of fumed silica were incorporated bystirring with a dissolver at 1500 to 4000 rpm, followed by furtherpredispersing over a period of five minutes at 2000 rpm. After that,final dispersion took place with cooling (<30° C.) for 30 minutes, nowusing a rotor-stator dispersing apparatus at 10 000 rpm. To conclude,the dispersion was filtered through a 500 μm sieve.

Example D7

Dispersion based on fumed silica with a specific surface area of 300m2/g and quaternary silane system (CPTEO/TMEDA system from comparativeexample 1)

Comparative Example

560 g of fumed silica were incorporated by stirring with a dissolver at1500 to 5000 rpm into a mixture of 1156 g of deionized water, 58.3 g ofquaternary silane system (CPTEO/TMEDA), and 25.7 g of acetic acid (25percent strength by weight solution in water), and dispersing wascontinued at 2000 rpm for 5 minutes. This was followed by finaldispersing with a rotor-stator dispersing apparatus (Kinematica PolytronPT6100) over a period of 30 minutes at 10 000 rpm. To conclude, thedispersion was cooled and filtered through a 500 μm sieve.

Example D8

Inventive dispersion based on fumed silica with a specific surface areaof 300 m2/g and the solution from example 1

557 g of fumed silica were incorporated by stirring with a dissolver at1500 to 5000 rpm into a mixture of 885 g of deionized water and 58 g ofthe solution from example 1, and dispersing was continued at 2000 rpmfor 10 minutes. This was followed by dispersing with a rotor-statordispersing apparatus (Kinematica Polytron PT6100) over a period of 30minutes at 10 000 rpm. To conclude, the dispersion was filtered througha 500 μm sieve.

TABLE Physicochemical data of dispersions D5 to D8 Comparison InventionD5 D6 D7 D8 Solids content*⁾ % by wt. 22.0 30 33 39 Particle diameter**⁾nm 132 125 121 114 Viscosity***⁾ mPa s 5600 2800 3580 5380 *⁾afterdrying to constant weight at 125° C.; **⁾by dynamic light scattering(Horiba LB-500); ***⁾at 1000 1/s; 23° C.;

Besides fumed silica with a specific surface area (BET surface area 300m2/g), it is also possible to prepare dispersions of the invention onthe basis of other fumed silicas with a specific surface area, as shownby examples D9 to D12.

Examples D9 to D12 General Preparation Instructions (for Quantities SeeTable)

The fumed silica powder was incorporated by stirring with a dissolver at1500 to 5000 rpm into a mixture of 885 g of deionized water and thecorresponding amount of the solution from example 1, and dispersioncontinued at 2000 rpm for 10 minutes. Then a rotor-stator dispersingapparatus (Kinematica Polytron PT6100) was used for dispersing at 10 000rpm over a period of 30 minutes. To conclude, the dispersion wasfiltered through a 500 μm sieve.

TABLE Preparation parameters and physicochemical data of dispersions D9to D12 D9 D10 D11 D12 Fumed silica type m2/g 150 200 255 255 (BET)Quantity of fumed g 472 375 335 420 silica used Quantity of solution g26.1 27.7 31.5 39.5 from example 1 used Solids content*⁾ % by wt. 3530.2 28 32.6 Particle diameter**⁾ nm 159 150 145 140 Viscosity***⁾ mPa s68 58 45 125 *⁾after drying to constant weight at 125° C.; **⁾by dynamiclight scattering (Horiba LB-500); ***⁾at 1000 1/s; 23° C.;

Production of Papercoating Slips Example S1 Comparative Example

By means of a dissolver at 500 rpm, dispersion D1 was admixed with a 12percent strength by weight solution of polyvinyl alcohol PVA 235, fromKuraray Europe, and the system was stirred for 10 minutes. The amount ofPVA 235 added was such as to produce a ratio of silicon dioxide to PVA(dry) of 5:1 (or 6:1 for S9 and S10). To adjust the viscosity, water wasadded in an amount such as to give the solids content indicated in thetable. Then a 7 percent strength by weight solution of boric acid inwater was added. The amount of the boric acid was 12.5% by weight of theamount of the polyvinyl alcohol. Lastly, the glyoxal-containingcomposition “Cartabond TSI” from Clariant was added. The amountcorresponded to 4.8% by weight of the amount of the polyvinyl alcohol.

The viscosity of the inkjet papercoating slip was measured using aBrookfield viscometer after 24 hours.

Examples S2, S3, S4, and S9 to S12 were produced in the same way as forS1, but using the respective dispersions D2, D3, D4, and D9 to D12. Thesolids contents and viscosities of the papercoating slips are reproducedin table 4.

TABLE 3 Solids contents and viscosities of papercoating slips S1 to S4Comparative example as per invention S1 S2 S3 S4 from D1 D2 D3 D4 Solids% by wt. 17.5 22.6 23.1 24.3 content Viscosity*⁾ mPa s 3680 5350 34103200 *⁾Viscosity (Brookfield) at 100 rpm and 20° C.; measured after 24 h

TABLE 4 Solids contents and viscosities of papercoating slips S9-S12 asper invention S9 S10 S11 S12 from D9 D10 D11 D12 Solids content % by wt.25.1 24.3 22.9 23.1 Viscosity*⁾ mPa s 4210 2860 3410 2200

Production of the Inkjet Coating

Inventive papercoating slips S4 and S9 to S12 were applied to aphotographic base paper (thickness 300 μm) using a profiled doctor bar.The wet film thickness of the papercoating slip was 80 μm. The coatingwas dried at 105° C. over a period of 8 minutes. The application weightachieved was a uniform 22 g/m². The coated papers were printed on aCanon PIXMA iP6600D inkjet printer with very high resolution. Theevaluation of the print outcomes is reproduced in table 5.

TABLE 5 Evaluation*⁾ of the print outcomes S1 S2 S3 S4 S9 S10 S11 S12Slip intensity 2 2 2 2 3 2.5 2 2 Resolution 2.5 2 2 2 3 3 2.5 2 Slipflow**⁾ 1.5 1 1 1 3 2.5 2 2.5 Slip shift 1.75 1.5 1.5 1.5 3 2.5 1.75 1.5Gloss***⁾ 45.1 43.5 43.1 45.3 30.1 39.8 42.3 45.3 *⁾Best score 1, worstscore 6; **⁾bleeding; ***⁾at 60° viewing angle

1. A quaternary-amino alcohol-functional, organosilicon compound,comprising: a quaternary-amino alcohol-functional silanol andquaternary-amino alcohol-functional siloxanol oligomers withSi—O-crosslinked structural elements, which form structures that arecatenate, cyclic, crosslinked, or any combination thereof and which areobtained by a process comprising reacting a silane of formula II,formula IV, or both or at least one hydrolysis, condensation, orco-condensation product starting from silanes of formula II, or IV, orboth, water, and at least one amino alcohol of formula III andoptionally at least partially removing a hydrolysis alcohol formedthereby from the system:(R¹O)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂Hal]_(1+y)  (II),[HO—(CH₂)_(m)—]_(z)N(R⁴)_(3-z)  (III),(R¹O)_(3-x-y)(R²)_(n)Si[R³)_(n)CH₂—N⁺[—(CH₂)_(m)OH]_(z)(R⁴)_(3-z)]_(1+y)·(1+y)[Hal⁻]  (IV),wherein at least one structure of the quaternary-aminoalcohol-functional, organosilicon compound is of formula I:(R¹O)[(R¹O)_(1-x-y)(R²)_(x)Si(C⁺)_(1+y)O]_(a)R¹ [a·(1+y)]Hal⁻  (I) eachC⁺ is independently a group of formula V:[—(R³)_(n)CH₂—N⁺[—(CH₂)_(m)OH]_(z)(R⁴)_(3-z)]_(1+y)  (V), each R¹ isindependently substantially hydrogen or a linear, branched, or cyclicalkyl group having from 1 to 8 C atoms in formula I, and isindependently a hydrogen, a linear, branched, or cyclic alkyl grouphaving from 1 to 8 C atoms, or an aryl, arylalkyl, or acyl group informulae II, III, and IV, each R² is a linear, branched, or cyclic alkylgroup having from 1 to 8 C atoms or an aryl, arylalkyl, or acyl group,each R³ is independently a linear, branched, or cyclic alkylene grouphaving from 1 to 18 C atoms, each R⁴ is independently a group comprisingC1 to C16 atoms, each n is independently 0 or 1, each m is independentlyan integer between 1 and 16, each z is independently 1 or 2 or 3, eachHal is independently chloro or bromo, each x is independently 0 or 1 informulae I and V and is independently 0, 1, or 2 in formulae II, III,and IV, each y is independently 0 or 1 in formulae I and V and isindependently 0, 1, or 2 in formulae II, III, and IV, (x+y) is 0 or 1 informulae I and V and is independently 0, 1, or 2 in formulae II, III,and IV, and a is greater than or equal to
 1. 2. A process for preparinga composition that comprises a quaternary-amino alcohol-functional,organosilicon compound that comprises a quaternary-aminoalcohol-functional siloxanol oligomer, the process comprising: reactinga component A with a component B in the presence of water, andoptionally at least partly removing a resultant hydrolysis alcohol,wherein component A is: (i) at least one haloalkyl-functionalalkoxysilane of formula II:(R¹O)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂Hal]_(1+y)  (II), (ii) a hydrolysisor condensation product of at least one alkoxysilane of formula II, or(iii) a mixture of at least one alkoxysilane of formula II and ahydrolysis product, a condensation product, or both of at least onealkoxysilane of formula II; component B is of formula III:[HO—(CH₂)_(m)—]_(z)N(R⁴)_(3-z)  (III); each R¹ is independently ahydrogen, a linear, branched, or cyclic alkyl group having from 1 to 8 Catoms, or an aryl, arylalkyl, or acyl group; each R² is independently alinear, branched, or cyclic alkyl group having from 1 to 8 C atoms or isan aryl, arylalkyl, or acyl group; each R³ is a linear, branched, orcyclic alkylene group having from 1 to 18 C atoms; n is 0 or 1; Hal ischloro or bromo; x is 0, 1, or 2; y is 0, 1, or 2; (x+y) is 0, 1, or 2;each R⁴ is independently a group comprising C1 to C16 atoms; m is aninteger between 1 and 16; and z is 1 or 2 or
 3. 3. The process asclaimed in claim 2, further comprising: hydrolyzing a product of thereacting in the presence of a defined amount of water.
 4. The process ofclaim 2, wherein component B comprises N,N-dimethylethanolamine,N,N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolaminetriethanolamine, or any mixture thereof.
 5. The process of claim 2,wherein an amount of water present in the reacting is from 0.5 to 500mol of water per mole of silicon atoms present in component A.
 6. Theprocess of claim 2, wherein the reacting comprises continuously ordiscontinuously metering water to component A, optionally in a mixturewith component B, or to a quaternary-amino alcohol-functional,organosilicon compound of formula IV:(R¹O)_(3-x-y)(R²)_(n)Si[R³)_(n)CH₂—N⁺[—(CH₂)_(m)OH]_(z)(R⁴)_(3-z)]_(1+y)·(1+y)[Hal⁻]  (IV).7. The process of claim 2, wherein the reacting comprises addingportionwise 0.5 to 4.0 mol of water per mole of silicon atoms.
 8. Theprocess of claim 2, wherein the reacting is in the presence of asolvent.
 9. The process of claim 2, wherein a pressure of the reactingis from 1 mbar to 100 bar, and a temperature of the reacting is from 20to 150° C.
 10. The process of claim 2, further comprising: removingvolatile solvent and optionally a group that is capable of hydrolyzingto volatile solvent down to a level in an overall reaction compositionof below 12% by weight to 0% by weight.
 11. The process of claim 2,wherein component A comprises at least one silicon compound selectedfrom the group consisting of 3 chloropropyltrimethoxysilane,3-chloropropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane,3-chloropropylmethyldiethoxysilane, 3-chloropropyldimethylethoxysilane,3-chloropropyldimethylmethoxysilane, and any hydrolysis or condensationproduct thereof.
 12. The process of claim 2, wherein the haloalkyl groupof component A and the tertiary nitrogen of component Bare present inthe reacting in a molar ratio of from 2:1 to 1:100.
 13. The process ofclaim 2, comprising: introducing component A together with a solvent andwater, adding component B, at least partly removing hydrolysis alcohol,and adding water; introducing component A and adding a solvent, addingwater, adding component B, at least partly removing hydrolysis alcohol,and adding water; introducing component A and adding a solvent, addingwater, at least partly removing hydrolysis alcohol thereafter addingcomponent B, at least partly removing hydrolysis alcohol, adding water,at least partly removing hydrolysis alcohol, and adding water; reactingcomponent A with component B at elevated temperature, adding furthercomponent B, subsequently a adding water, at least partly removinghydrolysis alcohol, and adding water; introducing component A and addinga solvent, adding water, at least partly removing hydrolysis alcohol,subsequently adding component B, adding water at elevated temperature,at least partly removing hydrolysis alcohol and optionally adding water;or introducing component A together with a solvent and adding water, atleast partly removing hydrolysis alcohol, adding component B, at leastpartly removing hydrolysis alcohol, and adding water.
 14. The process ofclaim 2, further comprising: adjusting a reaction composition by addingwater to a viscosity of less than 1500 mPa s.
 15. A quaternary-aminoalcohol-functional organosilicon compound of formula IV:(R¹O)_(3-x-y)(R²)_(n)Si[R³)_(n)CH₂—N⁺[—(CH₂)_(m)OH]_(z)(R⁴)_(3-z)]_(1+y)·(1+y)[Hal⁻]  (IV),wherein each R¹ is independently a hydrogen, a linear, branched, orcyclic alkyl group having from 1 to 8 C atoms, or an aryl, arylalkyl, oracyl group, each R² is a linear, branched, or cyclic alkyl group havingfrom 1 to 8 C atoms or an aryl, arylalkyl, or acyl group, each R³ isindependently a linear, branched, or cyclic alkylene group having from 1to 18 C atoms, each R⁴ is independently a group comprising C1 to C16atoms, each n is independently 0 or 1, each m is independently aninteger between 1 and 16, each z is independently 1 or 2 or 3, each Halis independently chloro or bromo, each x is independently 0, 1, or 2,each y is independently 0, 1, or 2, and (x+y) is independently 0, 1, or2.
 16. The process of claim 2, wherein the quaternary-aminoalcohol-functional, organosilicon compound is a compound of formula IV:(R¹O)_(3-x-y)(R²)_(n)Si[R³)_(n)CH₂—N⁺[—(CH₂)_(m)OH]_(z)(R⁴)_(3-z)]_(1+y)·(1+y)[Hal⁻]  (IV),wherein each R¹ is independently a hydrogen, a linear, branched, orcyclic alkyl group having from 1 to 8 C atoms, or an aryl, arylalkyl, oracyl group, each R² is a linear, branched, or cyclic alkyl group havingfrom 1 to 8 C atoms or an aryl, arylalkyl, or acyl group, each R³ isindependently a linear, branched, or cyclic alkylene group having from 1to 18 C atoms, each R⁴ is independently a group comprising C 1 to C16atoms, each n is independently 0 or 1, each m is independently aninteger between 1 and 16, each z is independently 1 or 2 or 3, each Halis independently chloro or bromo, each x is independently 0, 1, or 2,each y is independently 0, 1, or 2, and (x+y) is independently 0, 1, or2.
 17. A composition, comprising: a quaternary-amino alcohol-functional,organosilicon compound and water, wherein the composition is obtained bythe process of claim
 2. 18. The composition as claimed in claim 17,wherein a solids content in the composition is from 0.1% to 99.9% byweight, with all constituents in the composition totaling 100% by weightin total.
 19. The composition of claim 17, wherein a total nitrogencontent of the composition is from 0.1% to 15% by weight for a viscosityof 1 to 100 mPa s, and optionally for a pH in the range of from 5.0 to11.0.
 20. The composition of claim 17, further comprising: a pigment,filler, binder, crosslinker, optical brightener, coating auxiliary,other auxiliary, or any combination thereof.
 21. (canceled)